In this work, the effect of platinum percentage on the carbon support of commercial catalyst for electrodes to be used in a Polybenzimidazole (PBI)-based PEMFC has been studied. Three percentages were studied (20, 40 and 60%). In all cases, the same quantity of PBI in the catalyst layer was added, which is required as a 'binder'. From Hg porosimetry analyses, pore size distribution, porosity, mean pore size and tortuosity of all electrodes were obtained. The amount of mesopores gets larger as the platinum percentage in the catalytic layer decreases, which reduces the overall porosity and the mean pore size and increases the tortuosity. The electrochemical characterisation was performed by voltamperometric studies, assessing the effective electrochemical surface area (ESA) of the electrodes, by impedance spectroscopy (IS), determining the polarisation resistance, and by the corresponding fuel cell measurements. The best results were obtained for the electrodes with a content of 40% Pt on carbon, as a result of an adequate combination of catalytic activity and mass transfer characteristics of the electrode. It has been demonstrated that the temperature favours the fuel cell performance, and the humidification does not have remarkable effects on the performance of a PBI-based polymer electrolyte membrane fuel cell (PEMFC). © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.